Gutiérrez Hernández, SaraTomás Gamasa, María2022-06-212022-06-212022Chem. Sci., 2022, 13, 6478-6495http://hdl.handle.net/10347/28827Translating the power of transition metal catalysis to the native habitats of enzymes can significantly expand the possibilities of interrogating or manipulating natural biological systems, including living cells and organisms. This is especially relevant for organometallic reactions that have shown great potential in the field of organic synthesis, like the metal-catalyzed transfer of carbenes. While, at first sight, performing metal carbene chemistry in aqueous solvents, and especially in biologically relevant mixtures, does not seem obvious, in recent years there has been a growing number of reports demonstrating the feasibility of the task. Either using small molecule metal catalysts or artificial metalloenzymes, a number of carbene transfer reactions that tolerate aqueous and biorelevant media are being developed. This review intends to summarize the most relevant contributions, and establish the state of the art in this emerging research fieldeng© 2022 The Author(s). Published by the Royal Society of Chemistry. This Open Access Article is licensed under a Creative Commons Attribution-Non Commercial 3.0 Unported LicenceAtribución-NoComercial 4.0 Internacionalhttp://creativecommons.org/licenses/by-nc/4.0/journal article10.1039/d2sc00721e1742-2183open access